CN106179222A - A kind of magnetic green material is burnt and preparation method thereof - Google Patents

A kind of magnetic green material is burnt and preparation method thereof Download PDF

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CN106179222A
CN106179222A CN201610655743.1A CN201610655743A CN106179222A CN 106179222 A CN106179222 A CN 106179222A CN 201610655743 A CN201610655743 A CN 201610655743A CN 106179222 A CN106179222 A CN 106179222A
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burnt
magnetic
biomass
preparation
flue gas
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赵永椿
杨建平
张军营
郑楚光
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Huazhong University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/027—Compounds of F, Cl, Br, I
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Oil, Petroleum & Natural Gas (AREA)
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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract

The invention discloses the preparation method that a kind of magnetic green material is burnt, it comprises the following steps: biomass material is dried and uses crusher in crushing sieve, it is thus achieved that biological particles raw material；Biomass material is immersed FeCl3In aqueous solution, and mechanical agitation, it is thus achieved that prepare the burnt presoma of magnetic bio and leach dry；Its matter is placed in biomass pyrolysis furnace, at N without interruption2Under the conditions of, it is heated to 500 800 DEG C, and keeps steady temperature 30 120 minutes, then, at lasting N2Under naturally cool to room temperature i.e. to obtain described magnetic bio burnt.The invention also discloses corresponding magnetic green material burnt.Three steps of activation of the preparation of biomass char, the load of magnetic-particle and biomass char are integrated by the method for the present invention, simplify building-up process, and the magnetic-particle loaded is more firm with biology Jiao bonding, difficult drop-off, improve biological burnt reactivity largely, substantially increase the removal efficiency of simple substance tribute in flue gas.

Description

A kind of magnetic green material is burnt and preparation method thereof
Technical field
The invention belongs to Mercury In Coal Combustion Flue Gas removing sulfuldioxide field, be specifically related to a kind of for removing coal-fired flue-gas Elemental Mercury The burnt preparation method of magnetic green material.
Background technology
The a investigation report that United Nations Environment Programme issues for 2013 is pointed out, coal-burning power plant is topmost artificial hydrargyrum One of polluter.Hydrargyrum is one of heavy metal element that environment toxic is the strongest, and it has persistency, long-distance migration and biology Enriching, all has the biggest harm to ecological environment and human health." Minamata pact " is that the whole world is first passes through legally binding Limit the international convention of mercury emissions, hydrargyrum is used and discharge is made that and clearly limits, and establish reduction of discharging timetable.Pact is raw After effect, China will face huge hydrargyrum emission reduction.Research and develop efficient, economic coal-burning power plant's demercuration technology, can not only conscientiously subtract Few mercury contaminants is to ecological environment and the harm of human health, and can effectively alleviate China and fulfil the pressure of hydrargyrum reduction of discharging international convention Power.
Activated carbon spraying technique is known as being maximally efficient coal-fired flue-gas hydrargyrum release control technology in the world, but, This technical operation cost is the highest, limits its popularization and application at home.The hydrargyrum in efficient absorption material removal flue gas is utilized to be The most promising current technology.
It is concentrated mainly on currently for the research of demercuration adsorbing material and changes raw material, use different activation method, no The aspects such as same modifying agent and method of modifying.Biomass char is the carbon that a kind of biomass are decomposed under high temperature, oxygen free condition Matter solid matter, has abundant pore structure and surface functional group, is widely used as in the field such as gas purification, sewage disposal Adsorbing material.
Such as Chinese patent 201510490088.4 discloses the preparation method that a kind of magnetic bio is burnt, and it is first suitably Temperature and pyrolysis way under completely cut off air thermal dissociation biomass and obtain activated coke, then by determining mol ratio (Fe2+/Fe3+=1/2) Fe2+And Fe3+, rapid precipitation direct with NaOH or ammonia is distributed in biological burnt substrate, prepares Fe3O4/ biological burnt.Should Method uses chemical coprecipitation method by Fe3O4Load to biomass char surface, be divided into and produce biomass char and load Fe3O4/ two Step completes, and preparation process is complicated, Fe3O4/ generation process can not regulate and control, and easily occurs loading the problems such as uneven and particle agglomeration. It addition, the biological burnt demercuration performance synthesized is relatively low, need to pass through modified or activate to promote its demercuration efficiency, this can cause magnetic green The preparation process of material Jiao is more complicated.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of single for removing in coal-fired flue-gas The preparation method that the magnetic green material of matter hydrargyrum is burnt, the method is by the preparation of biomass char, the load of magnetic-particle and biomass Burnt three steps of activation are integrated, and simplify building-up process, and the magnetic-particle that the method is loaded glues with biology Jiao Knot is more firm, difficult drop-off, simultaneously FeCl3Catalytic action can be played, promote development and the surface official of biological burnt hole The generation that can roll into a ball, improves biological burnt reactivity largely, substantially increases the removal efficiency of simple substance tribute in flue gas.
For achieving the above object, the present invention provides a kind of magnetic green material Jiao's for removing elemental mercury from coal-fired flue gas Preparation method, it comprises the following steps:
(1) it is dried to remove contained humidity by biomass material；
(2) dried biomass material is used crusher in crushing, and sieve, it is thus achieved that the particle diameter biology less than 0.5mm Matter particulate material；
(3) biomass material described in step (2) is immersed FeCl3In aqueous solution, and mechanical agitation so that FeCl3Negative It is loaded in described biomass, it is thus achieved that prepare the presoma that magnetic bio is burnt, i.e. loaded FeCl3Biomass；
(4) the magnetic bio Jiao's presoma obtained in step (3) is leached and is dried；
(5) magnetic bio Jiao's presoma dried in step (4) is placed in biomass pyrolysis furnace, at N without interruption2 Under the conditions of, it is heated to 500-800 DEG C, and keeps steady temperature 30-120 minute, then, at lasting N2Nature under atmosphere It is cooled to room temperature and i.e. obtains described magnetic bio Jiao.
By such scheme, the present invention uses FeCl3As magnetic-particle presoma, first by powdered biomass at FeCl3 Solution impregnates certain time, makes FeCl3Load to biological surface, it is thus achieved that prepare the presoma FeCl that magnetic bio is burnt3/ raw Material, through dried, is pyrolyzed FeCl at suitable temperature and isolation air ambient3/ biomass obtain magnetic active bio Matter is burnt, the method compared with prior art, by the preparation of biomass char, the load of magnetic-particle and the activation of biomass char Three steps are integrated, and simplify building-up process, and the magnetic-particle that the method is loaded is more firm with biology Jiao bonding Gu, difficult drop-off, simultaneously FeCl3Catalytic action can be played, promote development and the life of surface functional group of biological burnt hole Become, improve biological burnt reactivity largely, substantially increase the removal efficiency of simple substance tribute in flue gas.
As present invention further optimization, described heating-up temperature is 600 DEG C, and heating rate is 5 DEG C/min, and keeps permanent Fixed temperature 30 minutes.
As present invention further optimization, described FeCl3Aqueous solution is 10-30ml/g with the ratio of biomass, preferably For 20ml/g.
As present invention further optimization, described FeCl3The concentration of aqueous solution is 10%-30%, preferably 20%.
As present invention further optimization, described mixing time is 2-4h, preferably 2h.
As present invention further optimization, described biomass material includes Cortex Populi dividianae wood flour, pinaster wood flour, rice husk, cotton Bar etc..
As present invention further optimization, the baking temperature of described biomass material is 80-120 DEG C, preferably 105 ℃。
As present invention further optimization, the drying time of described biomass material is 5-15 hour, and preferably 12 is little Time.
As present invention further optimization, the screening criteria of described biomass material is 20-40 mesh, preferably 32 mesh.
As another aspect of the present invention, it is provided that a kind of magnetic green material for removing elemental mercury from coal-fired flue gas is burnt The magnetic green material for preparing of preparation method burnt.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it is possible to show under acquirement Benefit effect:
(1) present invention uses FeCl3As magnetic-particle presoma, by powdered biomass at FeCl3In solution, dipping is certain Time, make FeCl3Load to biological surface, it is thus achieved that prepare the presoma FeCl that magnetic bio is burnt3/ biomass, through being dried After, at suitable temperature and isolation air ambient, it is pyrolyzed FeCl3It is burnt that/biomass obtain magnetic active bio matter, and the method will Three steps of the activation of the preparation of biomass char, the load of magnetic-particle and biomass char are integrated, and simplify and synthesize Journey, and the magnetic-particle that the method is loaded is more firm with biology Jiao bonding, difficult drop-off.
(2) in technical scheme, FeCl3Can play catalytic action, promote biological burnt hole development and The generation of surface functional group, improves biological burnt reactivity largely, substantially increases the removing of simple substance tribute in flue gas Efficiency.
Accompanying drawing explanation
Fig. 1 is that a kind of magnetic green material for removing elemental mercury from coal-fired flue gas of the embodiment of the present invention is burnt and preparation The process flow diagram related in method；
Fig. 2 (a) be a kind of magnetic green material for removing elemental mercury from coal-fired flue gas of the embodiment of the present invention burnt and The microscopic appearance that magnetic bio prepared by preparation method is burnt；
Fig. 2 (b) be a kind of magnetic green material for removing elemental mercury from coal-fired flue gas of the embodiment of the present invention burnt and The microscopic appearance that magnetic bio prepared by preparation method is burnt；
Fig. 2 (c) be a kind of magnetic green material for removing elemental mercury from coal-fired flue gas of the embodiment of the present invention burnt and The microscopic appearance that magnetic bio prepared by preparation method is burnt；
Fig. 3 is that a kind of magnetic green material for removing elemental mercury from coal-fired flue gas of the embodiment of the present invention is burnt and preparation The performance curve that magnetic bio prepared by method is burnt；
Fig. 4 is that a kind of magnetic green material for removing elemental mercury from coal-fired flue gas of the embodiment of the present invention is burnt and preparation The demercuration efficiency curve that magnetic bio prepared by method is burnt.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, right The present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, not For limiting the present invention.As long as additionally, technical characteristic involved in each embodiment of invention described below that The conflict of not constituting between this just can be mutually combined.
Embodiment 1
A kind of preparation method of magnetic green material Jiao for removing elemental mercury from coal-fired flue gas of the present embodiment, the method Specifically comprise the following steps that
(1) choose typical biomass material Cortex Populi dividianae wood flour, at 105 DEG C, be dried 12h to remove contained humidity；Subsequently Dried biomass material is used crusher in crushing and uses 32 mesh (0.5mm) standard screen to sieve, it is thus achieved that particle diameter is less than The biological particles raw material of 0.5mm；
(2) weigh 3g Cortex Populi dividianae wood flour to be placed in glass beaker, add 60mlFeCl3Solution and the ratio of Cortex Populi dividianae wood flour It is the FeCl of 20% for 20ml/g, concentration3Solution, after mechanical agitation 2h, has i.e. loaded FeCl by magnetic bio Jiao's presoma3's Cortex Populi dividianae wood flour (FeCl3/ Cortex Populi dividianae wood flour) leach, at 105 DEG C, it is dried 12h；
(3) by dried FeCl3/ Cortex Populi dividianae wood flour is placed in biomass pyrolysis furnace, at N without interruption2Under the conditions of, will It is heated to 600 DEG C from 30 DEG C, and heating rate is 5 DEG C/min, keeps steady temperature 30min when temperature rises to 600 DEG C, so After, at lasting N2Naturally cool to room temperature under atmosphere and i.e. obtain described magnetic bio Jiao.
Microscopic appearance as burnt in the magnetic bio that Fig. 2 (a) is acquisition, in its magnetic property such as accompanying drawing 3 shown in (a).Microcosmic shape Looks figure has shown in biological burnt surface uniform load magnetic-particle, and meanwhile, magnetic bio Jiao of synthesis has stronger magnetic, full 59.8emu/g is reached with the intensity of magnetization.Therefore, magnetic-particle successfully can be loaded to biological burnt surface by the method so that it is have Stronger magnetic, it is simple to it separates and recovers from flying dust.
The Elemental Mercury magnetic adsorbent of above-mentioned preparation is carried out combustion product gases demercuration performance evaluation, and experiment condition is as follows:
Flue gas composition is 4%O2, 12%CO2, 10ppmHCl, 800ppmSO2, 100ppmNO, 50ug/m3Hg0,5%H2O, Balance Air is N2, this flue gas composition is typical case's coal-burning boiler tail flue gas concentration of component.Reaction temperature is 140 DEG C, removes for electrostatic Flue-gas temperature before dirt device or sack cleaner.Experimental result shows that this adsorbent reaches 90.6% to the removal efficiency of Elemental Mercury, as In Fig. 4 shown in curve (a).Simultaneously as contrast, biological Jiao not having carried magnetic granule is also carried out demercuration performance evaluation, Find that its demercuration efficiency is only 11.5%, such as curve (d) in Fig. 4.Therefore, the method can very great Cheng while magnetized biological Jiao Its reactivity is improved on degree.
Embodiment 2
A kind of preparation method of magnetic green material Jiao for removing elemental mercury from coal-fired flue gas of the present embodiment, the method Specifically comprise the following steps that
(1) choose typical biomass material pinaster wood flour, at 105 DEG C, be dried 12h to remove contained humidity；Subsequently will Dried biomass material uses crusher in crushing and uses 32 mesh (0.5mm) standard screen to sieve, it is thus achieved that particle diameter is less than 0.5mm Biological particles raw material；
(2) weigh 4g Cortex Populi dividianae wood flour to be placed in glass beaker, add 40mlFeCl3Solution and the ratio of Cortex Populi dividianae wood flour It is the FeCl of 10% for 10ml/g, concentration3Solution, after mechanical agitation 2h, has i.e. loaded FeCl by magnetic bio Jiao's presoma3's Pinaster wood flour (FeCl3/ pinaster wood flour) leach, at 105 DEG C, it is dried 12h；
(3) by dried FeCl3/ pinaster wood flour is placed in biomass pyrolysis furnace, at N without interruption2Under the conditions of, by it Being heated to 600 DEG C from 30 DEG C, heating rate is 5 DEG C/min, keeps steady temperature 30min when temperature rises to 600 DEG C, then, At lasting N2Naturally cool to room temperature under atmosphere and i.e. obtain described magnetic bio Jiao.
Microscopic appearance as burnt in the magnetic bio that Fig. 2 (b) is acquisition, in its magnetic property such as Fig. 3 shown in curve (b).Microcosmic Shape appearance figure has shown in biological burnt surface uniform load magnetic-particle, and meanwhile, magnetic bio Jiao of synthesis has stronger magnetic, Saturation magnetization reaches 39.8emu/g.Therefore, magnetic-particle successfully can be loaded to biological burnt surface by the method so that it is tool There is stronger magnetic, it is simple to it separates and recovers from flying dust.
The Elemental Mercury magnetic adsorbent of above-mentioned preparation is carried out combustion product gases demercuration performance evaluation, and experiment condition is as follows:
Flue gas composition is 4%O2, 12%CO2, 10ppm HCl, 800ppmSO2, 100ppmNO, 50ug/m3Hg0,5% H2O, Balance Air is N2, this flue gas composition is typical case's coal-burning boiler tail flue gas concentration of component.Reaction temperature is 140 DEG C, for electrostatic Flue-gas temperature before cleaner unit or sack cleaner.Experimental result shows that this adsorbent reaches 85.2% to the removal efficiency of Elemental Mercury, As shown in curve (b) in Fig. 4.Simultaneously as contrast, biological Jiao not having carried magnetic granule is also carried out demercuration performance and has commented Valency, finds that its demercuration efficiency is only 11.5%, as shown in curve (d) in Fig. 4.Therefore, the method is while magnetized biological Jiao Can largely improve its reactivity.
Embodiment 3
A kind of preparation method of magnetic green material Jiao for removing elemental mercury from coal-fired flue gas of the present embodiment, the method Specifically comprise the following steps that
(1) choose typical biomass material cotton stalk, at 105 DEG C, be dried 12h to remove contained humidity；To be dried subsequently After biomass material use crusher in crushing use 32 mesh (0.5mm) standard screen sieve, it is thus achieved that particle diameter is less than the life of 0.5mm Material grains raw material；
(2) weigh 2g cotton stalk to be placed in glass beaker, add 20mlFeCl3Solution with the ratio of Cortex Populi dividianae wood flour is 10ml/g, concentration are the FeCl of 30%3Solution, after mechanical agitation 2h, has i.e. loaded FeCl by magnetic bio Jiao's presoma3Cotton Bar (FeCl3/ cotton stalk) leach, at 105 DEG C, it is dried 12h；
(3) by dried FeCl3/ cotton stalk is placed in biomass pyrolysis furnace, at N without interruption2Under the conditions of, by it from 30 DEG C being heated to 600 DEG C, heating rate is 5 DEG C/min, keeps steady temperature 30min when temperature rises to 600 DEG C, then, is holding Continuous N2Naturally cool to room temperature under atmosphere and i.e. obtain described magnetic bio Jiao.
As Fig. 2 (c) is the burnt microscopic appearance of the magnetic bio that obtained, in its magnetic property such as Fig. 3 shown in curve (c).Micro- Seeing shape appearance figure and shown in biological burnt surface uniform load magnetic-particle, meanwhile, magnetic bio Jiao of synthesis has stronger magnetic Property, saturation magnetization reaches 36.5emu/g.Therefore, magnetic-particle successfully can be loaded to biological burnt surface by the method so that it is There is stronger magnetic, it is simple to it separates and recovers from flying dust.
The Elemental Mercury magnetic adsorbent of above-mentioned preparation is carried out combustion product gases demercuration performance evaluation, and experiment condition is as follows:
Flue gas composition is 4%O2, 12%CO2, 10ppm HCl, 800ppm SO2, 100ppm NO, 50ug/m3Hg0,5% H2O, Balance Air is N2, this flue gas composition is typical case's coal-burning boiler tail flue gas concentration of component.Reaction temperature is 140 DEG C, for electrostatic Flue-gas temperature before cleaner unit or sack cleaner.Experimental result shows that this adsorbent reaches 78.4% to the removal efficiency of Elemental Mercury, As shown in curve (c) in Fig. 4.Simultaneously as contrast, biological Jiao not having carried magnetic granule is also carried out demercuration performance and has commented Valency, finds that its demercuration efficiency is only 11.5%, as shown in curve (d) in Fig. 4.Therefore, the method is while magnetized biological Jiao Can largely improve its reactivity.
In technical scheme, embodiment gives described FeCl3Aqueous solution is 20ml/ with the ratio of biomass G, 10ml/g, but the present invention is not limited to the ratio in above-described embodiment, FeCl3Aqueous solution is generally with the ratio of biomass 10-30ml/g, preferably 20ml/g, FeCl3The ratio of aqueous solution and biomass can also take 12ml/g, 15ml/g, 18ml/g, 23ml/g, 25ml/g, 28ml/g, 30ml/g etc., and FeCl3Aqueous solution is not limited to above-mentioned value, specifically with the ratio of biomass FeCl3Aqueous solution determines according to practical situation with the ratio of biomass.
In technical scheme, embodiment gives described FeCl3The concentration of aqueous solution is 20%, 10% and 30%, but the present invention is not limited to the concentration value in above-described embodiment, FeCl3The concentration of aqueous solution is 10%-30%, preferably It is 20%, FeCl3The concentration of aqueous solution can also take 13%, 15%, 18%, 23%, 25%, 28% etc., and FeCl3Water-soluble The concentration of liquid is not limited to above-mentioned value, concrete FeCl3The concentration of aqueous solution determines according to practical situation.
In technical scheme, giving described heating-up temperature in embodiment is 600 DEG C, but does not limit in the present invention Temperature value in above-described embodiment, heating-up temperature is 500-800 DEG C, preferably 600 DEG C, it is also possible to take 500 DEG C, 550 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C etc., and heating-up temperature is not limited to upper numerical value, and concrete heating-up temperature is according to actual needs Determine.
In technical scheme, giving the holding steady temperature time in embodiment is 30min, but in the present invention also The time value being not limited in above-described embodiment, keeping the steady temperature time is 30-120min, preferably 30min, it is also possible to take 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min etc., and when keeping steady temperature Between be not limited to above-mentioned value, concrete keep the steady temperature time to determine according to actual needs.
In technical scheme, embodiment gives described biomass material be Cortex Populi dividianae wood flour, pinaster wood flour, Cotton stalk, but the biomass material kind being not limited in the present invention in above-described embodiment, biomass material can also take birchwood At least one or multiple mixture etc., concrete biomass material root in bits, Lignum cinnamomi camphorae wood flour, phoenix tree wood flour, rice husk, straw Determine according to practical situation.
In technical scheme, giving described mixing time in embodiment is 2h, but is not limited in the present invention Time value in above-described embodiment, mixing time is 2-4h, preferably 2h, mixing time can also take 2.5 hours, 3 hours, 3.5 hours, 4 hours etc., and mixing time is not limited to above-mentioned value, and concrete mixing time determines according to practical situation.
It addition, the baking temperature of biomass material is also not necessarily limited to the value in above-described embodiment, typically can be 80-120 DEG C, It is preferably 105 DEG C, can be with 105 DEG C in Example, it is also possible to take 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C etc., and The baking temperature of biomass material is not limited to above-mentioned value, and the baking temperature of concrete biomass material determines according to practical situation.
It is also not necessarily limited to the value in above-described embodiment the drying time of biomass material, can be typically 5-15 hour, preferably Be 12 hours, can be with 12 hours in Example, it is also possible to take 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 13 hours, 14 hours, 15 hours etc., and it is not limited to above-mentioned value the drying time of biomass material, concrete biomass The drying time of raw material determines according to practical situation.
The screening criteria of biomass material is also not necessarily limited to the value in above-described embodiment, can be typically 20-40 mesh, is preferably 32 mesh, can take 32 mesh in above-described embodiment, it is also possible to take 20 mesh, 25 mesh, 30 mesh, 35 mesh, 40 mesh etc., and biomass material Screening criteria be not limited to above-mentioned value, the screening criteria of concrete biomass material determines according to practical situation.
A kind of magnetic green material for removing elemental mercury from coal-fired flue gas of the present invention is burnt and preparation method thereof, and it is the most former Reason is: load to the FeCl of biological surface3Hydrolysis can be occurred in dry run to generate Fe (OH)3, Fe (OH)3Can be at high temperature Pyrolytic process is converted into FeO (OH), and is further converted to Fe2O3.Biomass are decomposed raw under high temperature, isolation air ambient Become H2, the reducing substances such as CO, C. Fe2O3Fe can be generated by the reduction of above-mentioned reducing substances3O4, so that biological Jiao has magnetic Property.What is more important, is supported on the FeCl of biological surface3Catalytic action can be played, promote development and the table of hole The generation of face functional group, activation that therefore can be certain while giving biological Jiao.This process can be with following reaction Equation describes:
FeCl3+3H2O→Fe(OH)3+3HCl↑ (1)
Fe(OH)3→FeO(OH)→Fe2O3 (2)
3Fe2O3+4H2(CO,C)→2Fe3O4+4H2O(CO2,CO)↑ (3)
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention, not in order to Limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, all should comprise Within protection scope of the present invention.

Claims (10)

1., for removing the preparation method that the magnetic green material of elemental mercury from coal-fired flue gas is burnt, it comprises the following steps:
(1) it is dried to remove contained humidity by biomass material；
(2) dried biomass material is used crusher in crushing, and sieve, it is thus achieved that the particle diameter biomass less than 0.5mm Grain raw material；
(3) biomass material described in step (2) is immersed FeCl3In aqueous solution, and mechanical agitation so that FeCl3It is carried on In described biomass, it is thus achieved that prepare the presoma that magnetic bio is burnt, i.e. loaded FeCl3Biomass；
(4) the magnetic bio Jiao's presoma obtained in step (3) is leached and is dried；
(5) magnetic bio Jiao's presoma dried in step (4) is placed in biomass pyrolysis furnace, at N without interruption2Condition Under, it is heated to 500-800 DEG C, and keeps steady temperature 30-120 minute, then, at lasting N2Natural cooling under atmosphere Described magnetic bio is i.e. obtained burnt to room temperature.
The preparation side that a kind of magnetic green material for removing elemental mercury from coal-fired flue gas the most according to claim 1 is burnt Method, wherein, described heating-up temperature is 600 DEG C, and heating rate is 5 DEG C/min, and keeps steady temperature 30 minutes.
The preparation that a kind of magnetic green material for removing elemental mercury from coal-fired flue gas the most according to claim 1 and 2 is burnt Method, wherein, described FeCl3Aqueous solution is 10-30ml/g with the ratio of biomass.
4. burnt according to a kind of magnetic green material for removing elemental mercury from coal-fired flue gas according to any one of claim 1-3 Preparation method, wherein, described FeCl3The concentration of aqueous solution is 10%-30%.
5. burnt according to a kind of magnetic green material for removing elemental mercury from coal-fired flue gas according to any one of claim 1-4 Preparation method, wherein, described mixing time is 2-4h.
6. burnt according to a kind of magnetic green material for removing elemental mercury from coal-fired flue gas according to any one of claim 1-5 Preparation method, wherein, described magnetic bead particles size is 100-400 mesh.
7. burnt according to a kind of magnetic green material for removing elemental mercury from coal-fired flue gas according to any one of claim 1-6 Preparation method, wherein, described biomass material includes one or more in Cortex Populi dividianae wood flour, pinaster wood flour, rice husk and cotton stalk.
8. burnt according to a kind of magnetic green material for removing elemental mercury from coal-fired flue gas according to any one of claim 1-7 Preparation method, wherein, the baking temperature of described biomass material is 80-120 DEG C.
9. burnt according to a kind of magnetic green material for removing elemental mercury from coal-fired flue gas according to any one of claim 1-8 Preparation method, wherein, the drying time of described biomass material is 5-15 hour, and the screening criteria of described biomass material is 20-40 mesh.
10. utilize a kind of magnetic green material for removing elemental mercury from coal-fired flue gas according to any one of claim 1-9 The magnetic green material that burnt preparation method prepares is burnt.
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CN113797898A (en) * 2021-10-18 2021-12-17 青岛理工大学 Preparation method and application of magnetic adsorbent for efficiently removing elemental mercury and hydrogen sulfide

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Application publication date: 20161207